Activation of petroleum adsorbents



Sept. 7, 1948. T. P. SIMPSON EI'AL ACTIVATION OF PETROLEUM ADSORBENTS Filed Dec. 11, 1943 REFI PERCENT 64,950 01V 62/ Pateniedse i. 7, 1948 ACTIVATION OF PETROLEUM ADSORBENTS Thomas P. Simpson, John W. Payne, and Peter D. Valas, Woodbury, N. 1., alslgnors to Socony- Vacunm Oil Company, Incorporated. a corporation of New York Application December 11, 1948, Serial No. 513,938

l Claim. (Cl. 198-147) This invention relates to a method for improving the activity and prolonging the useful life of solid adsorbent materials used in the refining of petroleum products. The invention particularly relates to the regeneration of clays used in the refining of petroleum products.

Enormous quantities of clays are used throughout the petroleum industry as filtering and adsorbent means for refining petroleum products. In general three different methods are used for refining petroleum oils with clays. These methods are the percolation process wherein liquid oil is percolated through granules of the clay, the contact process wherein liquid oil is contacted with finely pulverized clay and the vapor process wherein oil vapors are passed through granules of the clay. In all these methods, after the clays have refined a certain amount of oil they become so contaminated with carbonaceous impurities collected from the oil that they must be regenerated or discarded. Usually the contact clays are discarded after the first use and once used vapor process clays are thereafter employed in percolation processes. Accordingly, in practice, generally only granular percolation clays are regenerated. Heretofore regeneration has been eil'ected principally by a chemical oxidation wh..:h universally consists of burning off the impurities.

In view of the fact that the petroleum products treated by percolation through solid adsorbents are combustible, it is evident that, when regeneration becomes necessary it is not the usual practice to pass the adsorbent directly to regeneration, either in the same container or in another operation, since the adsorbent carries a very considerable amount of the oil with which it has been in contact. If the oil is volatile, it is customarily removed by steaming. If it is a. heavy oil, it is customarily removed by washing with a lighter, volatile oil, the residue of which, in turn is also removed by steaming. This operation is called a "steam purge" and is common throughout the art to which this invention appertains.

In the past various methods have been used for carrying out the burning of granular spent clay. One of the first comprised spreading the clay on an open hearth and burning it. Today there are three principal methods in general use. In the first method the clay falls or cascades over baiiles set at about a 45 angle through a flue countercurrent to gases of combustion. In the second method the clay is regenerated in a rotary kiln slightly inclined from the horizontal. In the third method, which probably is the most commonly used, multiple hearth burners are employed. These multiple hearth furnaces or burners are substantially the same as used in the roasting of ore and are of either the Nichols- Herreshofl or Wedge type. In these burners the clay is slowly rabbled across each hearth, droppin from one to another until the bottom hearth is reached. In all of these conventionally used methods there is a progressive degradation in the efliciency of the clay with each burning and finally the clay must be discarded to waste since it is no longer capable of being regenerated sunlciently to warrant further treatment.

The co-pending application Serial No. 210,150 abandoned), tilled May 26, 1938, and Patent No. 2,245,531, issued June 10, 1941, of John W. Payne disclose and claim two other methods adapted for regenerating clay.

While undoubtedly progressive degradation in efllciency of clay type adsorbents results from the uncontrolled burning of contaminants deposited thereon, it appears, from experimental work, that this tendency is at least augmented because of the steamin of the clay prior to the burning oil of the contaminants, such wetting being an unavoidable incident of the steam purge.

Since clays which have had a different number of burnings by the present conventional processes have different efilcien-cies, they are kept separate and separately classified. In some of the larger refineries extensive inventories and bin facilities are required in order to maintain the clays according to their classification or efficiency. Not only does the large inventories of clay, bin facilities, etc., mean added expense but quite obviously the successive degradation in efliciency and the corresponding requirement of more clay increases the expense.

Most important amongst the disadvantages of the commonly used clay regeneration methods, however, is the fact the clay can only be regenerated a very limited number of times before its efllciency is so low that it does not pay to regenerate it, at which time the clay is thrown away to waste. In general, granular petroleum filter clays are only regenerated seven or eight times and practically never more than ten or ilfteen times, at which time their emciency is reduced to about 50% of the original and they are thrown away. As stated above, the nnely pulverized contact clays, e. g., 200 mesh or finer, which are less frequently used, are practically never regenerated.

In order to further stress the tremendous importance of the problem involved it might be pointed out that over the U. 8. there are roughly 5,000 tons of petroleum filter clay regenerated each day with the attendant degradation inefliciency accepted by the art. Furthermore each year the petroleum industry purchases about 225,000 tons of new iuller's earth alone. representing an expense oi over four million dollars. and discards to waste roughly 200,000 tons of clay that is considered too spent to warrant regeneration.

It is a well known fact that every heavy oil refinery in the country has large clumps of spent clays that have been thrown away to complete waste. In some cases this waste clay is left as a dump and in other cases it is used for filling in low land, sold for fertilizers, etc. However, in all cases there is this enormous discarding of spent clays. Such waste is accepted as a necessary evil of the process.

There have been a few suggestions from time to time in other fields that clays might be regenerated to higher efllciency. Likewise in the petroleum industry it has been suggested that a particular form of clay under very special condition might be regenerated to higher eillciency. However, the fact that other methods have not been taken up by the petroleum industry is believed conclusive that other known regeneration processes than those now used are not feasible for treatment of the clays used in refining petroleum or it is not obvious that they could be applied to regenerating petroleum clays. While such a fact is not usually so conclusive it is believed to be in the present case in view of the tremendous amounts of clay used and thrown away to waste each year as shown above and the increased amounts necessary because of the successive losses in efllclency as well as other attending dlsadvam tages. Certainly it cannot be maintained that one of the country's largest industries would go on year after year suffering the above-mentioned wastes and disadvantages if a remedy therefor was obvious.

It is an object of our present invention to provide a method oi improving the activity of solid adsorbent materials used in the refining of petroleum products.

Another object is to provide a method of regenerating refining clays used in the petroleum industry in such a manner that the regenerated clays are even more eillcient than the original fresh clay.

Still another object of the present invention is to provide a method 01' regenerating clays used in refining petroleum products in such a manner that the clays do not suffer progressive degradation in efilciency with each regeneration, regardless of whether they are subjected to steam purging or other similar treatment to the oxidation of contaminants which may be deposited thereon.

Still another object is to provide a method which is capable of always regenerating the refining clays used in the petroleum industry to a suillciently high efiiciency to warrant regeneration and hence eliminating the waste of d scarding spent clays.

A further object is to provide a method for regenerating reilning clays used in the petroleum industry which is capable of reclaiming spent clays which are now being thrown away to complete waste.

An important object of the present invention is to provide a method which is capable of sub- .iecting spent clays, whose efliciencles are so low that they would normally be discarded to waste since the present commonly used regenerating methods are not capable of regenerating the clays to a sumciently high emciency to warrant regeneration, to a regeneration process that regenerates such clays to a desirable eiilciency.

Still further object is to provide a process of increasing the useful life oi the clays which process is capable of regenerating discarded spent clay of the petroleum industry to an emciency greater than that of the original fresh clay.

Another object is to provide a method of improving the petroleum reflning activity of a, fresh clay which has never been used bei'ore for refining petroleum products.

The present invention is based upon the important discovery that solid adsorbent materials such as clays used in refining petroleum products when contaminated or coated with carbonaceous petroleum products may be subjected to a carbonizing treatment which converts at least a portion of the petroleum products on the clay to a. deposit of carbon or essentially carbon creating an activated carbon layer thereon which gives the clay an enhanced petroleum refining activity. While it may be found desirable at each activation treatment or at intermittent treatments as the carbon content builds up to burn oil part 0! the petroleum product or carbon associated with the clay. the essential feature is that at each treatment at least a suflicient portion of the petroleum product associated with the clay is carbonized on the clay to a highly active carbon deposit to give the clay an enhanced refining activity. Thus contrary to the conventional regeneration processes of today which regard the carbonaceous impurities as a complete evil which clogs the p rous structure of the adsorbent and which must be completely burned off, the present invention makes use of at least a portion of this carbonaceous impurity by converting it to an activated carbon deposit on the clay.

The method for regenerating the clay for our process necessitates but little change in the present methods and means for regenerating clays. While other methods might be devised which incorporate the principles of our invention it is preferred to operate in a manner closely analogous to present burning method thus increasing the commercial acceptability oi the process.

Accordingly our regeneration may be carried out by heating the spent clays under the well known clay burning conditions of time, temperature. etc., but with control of the oxygen content or the atmosphere contacting the clay in such manner that the regenerated clay carries an activated carbon deposit rather than having all the impurities burned on.

It has been found that the temperature or our carbonizing regenerating process may b varied over a considerably wider range than is desirable in the clay bumlng regeneration methods now being used. Thus in our process the temperatures required for destructive distillation of the adsorbent petroleum products may vary from that necessary to promote incipient distillation of the petroleum product up to that which will be damaging to the clay under the circumstances. In the conventional regenerating methods wherein the impurities are burned from the clay an extremely close temperature control should be maintained as otherwise ineiiicient regeneration or damage to the clay results. The temperature for clay burning should preferably be maintained substantially within the range of 950-1150 F. However, in the present process it has been found the carbonization regeneration may b effected, for instance, within the range of about 900-1500 R, with equal success. This is of itself an advantage since the regeneration may be eflected with less chances of damaging the clay. The optimum time of heating when carbonizing varies from a few seconds at 1500* F. to several minutesat 1000 F,

The important feature in regenerating by the present process is proper control of the atmosphere in the regenerating or activating zone. The essential feature is to sufficiently restrict the amount of air or other carbon oxidizing gas in the zone that complete combustion of oxidation of the petroleum products will not occur. It has been found that carbonization takes place both in the complete absence of air or other carbon oxidizing gas and also in the presence of limited amounts of air provided the quantity is insufficient to oxidize the activated carbon from the clay. Thus in carrying out the carbonization the heating zone may be completely sealed and no air admitted or a limited amount of air may be admitted with or without other inert gases. It has also been found that, if desired, steam may be admitted to the carbonizing zone. The presence of steam facilitates the removal of hydrocarbon vapors and reduces the rate of carbon build-up on the clay. For some oils it appears carbonizing in the presence of steam gives slightly better resuits, however, in general, reactivation is approximately the same for all the above carbonizing methods.

In practice we prefer to carry out our process in apparatuses such as disclosed in the two Patents No. 2,226,578, issued December 31, 1940, and No. 2,244,724, issued June 10, 1941, respectively, of John W. Payne, wherein the clay is passed through the regenerating zone in close proximity to a liquid heat transfer medium. These apparatuses have several construction and operating advantages over other known regenerating kilns. In regenerating clays by burning as is now commonly done in the art at extremely close temperature control should be maintained and for such regenerations the above mentioned Payne apparatuses are highly advantageous on this point alone. Furthermore, the apparatus disclosed in Patent No. 2,244,724 is well suited for regenerating the finely divided contact clays as well as the granular clays, the clays being carried through the apparatus suspended in a gaseous medium. However, as mentioned hereinabove the close temperature control of burning regenerations is not necessary in the present carbonizing process. Accordingly insofar as the degree of reactivation is concerned the present process may be carried out in other apparatuses such as the bafiled vertical flue, rotary kiln or multiple hearth kilns now in common use in the industry with equal success, the cays being passed through these kilns in the same manner in which they are under present burning methods, it being understood, of course, that in any apparatus used appropriate provision is made for controlling the amount of air or other combustion supporting gas admitted to the carbonizing zone. It is believed, however, that in any commercial set up it will be found desirable to do a certain amount of burning as well as carbonizing. Accordingly, it is preferable to employ one of the Payne apparatuses as then the one apparatus may be used for both the burning and the carbonizing. Otherwise, if it is desired to obtain the advantages in burning that may be given by the Payne apparatuses separate kilns must be used for the carbonlzing and the burning.

Thus far the manner of producing the carbon deposit on the solid inorganic adsorbent has been discussed, but little has been said of how much carbon should be left as an active carbon deposit on the clay or what the protective and refining activity effect of such a deposit will be. Since normally the steam purge directly follows a refining operation and thereafter the adsorbent is regenerated before further refining is undertaken, the effects of the steam purge will be first discussed and thereafter the refining activities of adsorbents regenerated according to the present invention.

Experiments on typical clay indicate that if contaminated percolation clays are wet with steam or water and then heated to normal regenerating temperatures of the order of 900 F. or higher, a loss of about 1% in decolorizing eiilciency results. Then. if the clay is cooled, revvet and then reheated a further 1% decrease in decoiorizing ei'liciency again results. In other words, repeated cycles of wetting, heating and cooling will each be accompanied by a 1% decrease in decolorizing efliciency. Since repeated cycles of this type are incident to the use of clays in decoiorizing when the clay is wetdurlng the steam purge, heated during the oxidation of the contaminants thereon and cooled during the decolorizing operation, it is evident that normal use will result in about a 1% loss in efllciency per cycle of employment. It has been demonstrated, however, that the presence of certain quantities of carbon on the clay will protect it from the detrimental effects of sequential wetting, heating and cooling. Typical experimental data to this effect is set out below; eificiency values being based on burned fullers earth as eflicient.

TABLE I Wsr'rmo AND Raf-mums or CLEAN AND CARBGNIZED Cans Clays after treatment Docolorizing Decoloritlng ell. of carcfl'. of clay Per cent hon-iree with carbon Clay treatment carbon clay, perthereon.

on clay cnlaimn percolation stock stock Sol. Acid Sol. acid ref. ref. ref. rci.

Fresh burned iullers earth 0.0 100 100 Fresh burned iuiler's earth after 20 wetting and healing cycles 0.0 79 71 carbonized fullers earth after 20 wetting and heating cycles 1 4.8 77 Do 8. 2 93 136 28) Do 12. 7 99 142 1 Cvcle-Wet clay, heat to i0m F. and cool.

I Clays were contaminated and carbonized during cycles.

It will be seen that these operations parallel the commercial handling of adsorbents in that clay is first treated with steam, as in the com- 7 mercial steam purge. it is next heated to high temperatures, as in the commercial burning or regeneration, and is then cooled. Just as in commercial practice prior to its return to the filtering percolation with the carbon still on it. In other words, while the carbon may be removed to see what the protective effect was, in use it may be desirable not to remove the carbon. knowing oi operation. In other words, with respect to course from the foregoing data that the protecsteaming. heating. and cooling each clay called tion is aiiorded. In order to clearly establish for by any horizontal line of the table is subthe surprising improvements which this invenlected to the equivalent of twenty complete cycles tion involves when the carbonized clay is used of commercial use. in percolation decolorizine. a substantial amount From the above it can be seen that the amount or data will be set forth herein. For convenience of carbon required to protect the clay varies certain criteria and notations used in these tests somewhat depending upon the oil stock processed will be explained at this point. All of the acthrough it. The ratio of decolorizing efliciency tivity tests are tests of the decolorizing efllciency to quantity of carbon by weight is expressed 01' the clay by the percolation method and the graphically in the figure oi drawing in which values are also based on fresh clay as being 100%. the abscissa represents percentage by weight of The number of the clay indicates the number carbon on clay and the ordinate represents per- 0! times it has been regenerated (by convencentage of decolorizing emciency. It will be tional burning or the present carbonizing as innoted that the graph has been prepared to illusdicated after the number). Various petroleum trate the table set out above. stocks were used in the tests and they are as The line in the drawing marked "Acid refined follows:

Stock s. c. Viscosity Crude Bouroo 1:35:33?

.880 245-254 130 F. Okla. City (Health) Duo Bol (solvent lot).

885 88-90 2l0 F do Do. an ns-im 210" F Do.

Do. .do Sulfuric Acid rei'. Coastal (Dlstillat Do.

.905 azo-aaoww'r'ill. Coastal Dist.)+Paraflln(Dist.) I Do.

.87!) W 210 F Pa. Brig t Btock+'Pa. Neutral Chlorer (solvent rei.).

lndlwtes that not y 15 the 3! P o ted As noted hereinabove the carbonizatlon may against degradation in emciency incident to 20 be effected (with certain restrictions) in variwetting-heating-cooling cycles. but that its clean 35 ous types of apparatuses and in the presence of burned eiiiciency for acid refined oils is actually various atmospheres. These statements may be enhanced if the ratio by weight of the carbon confirmed by the following tabular data:

TABLE II oonvelm Activity of Clay carbonized in Diii'erent Equipment 0118 Durnine, P B. r. (1. Stock Clay No. 3153 Closed Pill! Closed Pan A32: Rm awed in Mume in Muflie 0! Pat oi Pat. Tube in Bum d (With (Without 2,244 124 means Lead Bath Steam) Steam) (limited comma (No Air) Y Air) Air) Fresh Burned... 100 100 ii!) 100 100 100 No. 1. 84 m 166 100 174 No. 2 76 No. 69 No. 0. No.8 6| No.10 s1 Fresh Burned..- 100 No.4 70 Fresh Burned... 100 No. is

Fresh Burned... 100

No. 4. no

No.6 or

No. 6 so to the clay is in excess of about 2%%. 0n the 60 It will be seen from the above table that the other hand. the line marked "Solvent refined" activity obtained varies somewhat with the apin the drawing indicates that the maintenance paratuses and the atmospheres therein and also 01' emciency for that type of oil requires about as to the particular oil being refined. However, il /2% by weight of carbon before any appreciable in general the results are comparable and all advantage over the uncarbonized clay is noted 55 show tremendous improvement over the conand about 12% for the prevention of eiliciency ventional burning regeneration. The improveloss as compared to new clay. ment over conventional burning will be pointed The data illustrated in the drawing is of course out more in detail hereinafter.

concerned with the emciency of the clays upon It will be recalled that one 01 the principal clean burning after a series of wetting-heating- 70 objects oi the present invention was the regencooling cycles and as a consequence is illustraeration of clay to a higher activity than is obtive oi the protective eiIect of certain percentages tainable b present methods in common use. of carbon on the clay. However, a considerable That such object has been attained to a high amount of research has been conducted in condegree by the present invention can be seen nection with the activity of the clay ii used in clearly from the following data:

sesame 9 ram m Courua-rrv: Ymms hon Buuun m Cnlonmn Cur [Per cent peroolation emclenoy (without naphtha dilution Multiple wt b0 Hearth Stock Clay Percent iced Clay g fi Carbon Efl.

Fresh burned n 100 0 100 A N0. 10 55 8.0 2" Av. No.1 to N0. 10... M 5.0 193 Fresh burned 100 0 100 B 0. 50 B. 5 250 Av. No. l to N 63 5.5 246 Fresh burned 100 0 100 C No. ll 52 0.0 125 Av. No. l to No. II. 66 4.0 131 D N0. l0 66 e. 22) ill) 0 100 7B 4. 5 56 8B 2. 5 70 100 0 1m 50 8.0 U) 65 5.0 06 100 0 ill) 0 No. B 58 5. 6 77 Av.No.lto No.1... 69 2.5 8) Fresh burned 100 0 100 B No. l 88 il7 No.2 03 130 B6 130 From the second column of the above table it can be seen that the percentage by weight of carbon on the clay varies between 2.5 and 8. This has been found to be the range productive of greatest efliciency gains, and it should be noted that it lies within the range set out in the figure of drawing and described above in connection with protecting clays from the eflects of the steam purge.

The tremendous improvement and advancement of the art by the present process is apparent from the table. With all the oils treated (except one) the carbonized clay showed marked improvement over the corresponding burned clay. It is needless to point out the commercial advantage of such increased activity. For some reason, at present unknown, carbonized clay shows even much greater activity toward solvent refined oils than toward the oils which have been refined with sulfuric acid. It will be noted that on some of these solvent refined oils the activity oi the carbonized clay goes even above 200%. Furthermore that clays which have been burned 10 times and upon another burning regenera- 5 tion have an efilciency around 50, at which time they would usually be discarded to waste, may be regenerated by our carbonizing process and have their efliciency go up above 200%. This further important specific discovery with respect 10 to the solvent refined oils is covered in Patent 2,245,016, issued June 10, 1941.

It will also be noted from Table III that in general the activity oi the carbonized clay towards acid treated oils shows a marked improvement over burned clays even though the improvement is not as much as for solvent refined oils. In one case, stock E, the carbonized clay showed a slightly less activity than the burned clay. This exception cannot be explained, neverthe- 50 less there is a distinct advantage in carbonlzing the clay used on this oil. The less efliciency oi the carbonized clay on stock E is far oflset by the fact that when the carbonized clay reaches a low efilciency. which under present day practice would require its being thrown away. this clay may be carefully burned to remove the carbon and yield a clay which has substantially its original activity and which may be sent through further carbonizing and burning cycles thus indefinitely extending its life or usefulness. This same cycle procedure may be used on the clays for treating the other oils ifdesired including even the clays for treating the solvent refined oils, in fact, after many oarbonizations the carbon deposit on the clays may be so great that it is desired to burn of! part .or all even though the emciency is up fairly well. This process of regenerating clays by carbonizing and burning cycles forms the subject matter 01' Patent 2,299,258, issued October 20, 1942.

Another principal object of the present invention was to provide a method of regenerating clay wherein the clay did not suffer successive degradations in efllciency with each regeneration and 5 finally must be thrown away but rather could be regenerated to high efllciency indefinitely. That such object has been attained by the present process may be seen from the following data:

TABLE IV Stock A Pereo- Stock B Percolated to Lov. lated to Lov. Stock C I Stock 1" Clay Method of Reactivation g fi fig ag g gs smug Sol(ut)ion straight Sciatica Straight Straight Fr. Burned Clay per cent. 92 100 97 100 100 No. 5-10 Rel. Burned Clay Ava; 48 42 No. 7-10 Rel. Burned Clay Ave. 63 53 Carbonlzation:

No. 2 Fr. Clay..

No. 3 Fr. 0lay.

No. 4 Fr. Clay.

No. 5 Fr. Clay- No. 6 Fr. Cla

No. 7 Fr. Clay.

No. 8 Fr. Clay- No. 9 Fr. Ola

No. 11 Ft.

No. 1:! Fr.

No. 1! Fr. Clay N0. 16 Fr. Clay.

Average 1 Initial eolm' Lovibond l Initial color m Lovibond Ce 95 Lovibond git" C28.

| Initial 00101 4 Initial color 15 Lovibond M" C The above table shows that the successive deg- TABLE v radation in efllciency which is always obtained with burning regenerations is not obtained with our carbonizing but instead the activities come new "eucflmm back time after time to a high level. As men- 5 tioned hereinabove, under present day convenfigfigg'gg Ziggy; tional burning regenerations the clays are thrown Lov. Straight Loy. Straight away after 7 to 10 regenerations. From the above table it is seen that at 7 to 10 regenerations the gfff'ff'fffifff" lf f m I efllciency oi the clay is still at a very high level 10 Carbonllation nazdilifaloilillie'ry and that the efliciency stays at the high level g fj'g m gg ggmg g ggy upon further regenerations. Theoretically clays g' could be regenerated forever by our process: how- 0 y 131 no ever, by present methods and means of regeneraff {?f{ f; ?f i Refine m m tion there is about a 2% mechanical loss of clay 15 Cigbmiimlon bin-60131530 mit s from handling with each regeneration. Therefore o ggdiliiiibii'fid."ibl'fidfid antes I: the clay is lost through handling before it reaches Y l a point at which regeneration is not feasible. As its no the loss is about 2% per regeneration this would go m mean the clay could be regenerated in practice Germain-won 0 ol 0 en about 50 times. my m One of the most surprising and important fea- Average tures of the present invention is the fact that clays which have been regenerated by conventional burning methods until their efliciency is so low it no longer pays to regenerate them, i. e., they have been burned about 10 times and their efficiency is around 50% or 60%, may now be subjected to our carbonizing treatment and their eiilciency becomes greater than their eihciency as a fresh clay. More surprising still is the fact it is possible to reclaim these burned clays that have been thrown away. For instance, it is possible to bring in discarded clays oil the dumps at the refinery which, as explained above, have been thrown away because of their low eiflciency, and subject these discarded clays to our carbonizing process and bring their efliciency or activity up to a value which is greater than that possessed by the original fresh clay. In the case of discarded contact clays it has also been found feasible to convert same to granular clay by extrusion, e. g., forming 36 mesh granules, and carbonizing this "synthetic granular clay. The following data illustrates the type results that may be obtained in reclaiming discarded clays:

The data oi Table V also further evidences the fact that clays may be regenerated indefinitely by our process. For instance in the ninth carbonization the clay has had nineteen regeneratlons (10 burning and 9 carbonizing) and is efliciency is from 163 to 239%.

The tremendously important commercial aspects of all the features of our invention should be readily apparent from the foregoing data. The enormous savin which may be made by the present invention over presently used burning regeneration methods is obvious.

Since it may not be apparent from the data it might be well to state that carbonized or burned clays which have been used for refining acid treated oils may be subjected to a carbonizing treatment and then used for refining solvent refined olls and it is found that their activity for the solvent refined oils is of the extremely high nature of the clays shown in the tables.

The physical characteristics and oxidation stability of oils percolated through our carbonized clays are approximately the same as those of oils percolated to the same blend color through conventionally burned clays as is shown by Table VI.

TABLE VI Paormrms or Oms Placouim Taaolmn CM!- sornzrn AND PLAN! Bmunn Cums Color E U. V. 0

Stock Typezoi Cla V. I

Lovibond Story 1" 100' 210 (54" Cell) Cell) F. 1.

Fresh Burned Clay 55 56 No. 7-10 Plant Burned Clay 56 62 Fresh Clay Burned after 11 Carbonizatlons 52 4d Fresh Clay after 2 Carbonizations 55 62 Fresh Clay after 5 Carbonlzations 56 60 577 07. 3 0B Fresh Clay after 11 Carbonlrations H 66 62 579 67. 3 96 Fresh Clay after 14 Carbonitations .i 56 64 580 67. 7 9&8 No. in Plant Clay after 2 CarbonizatlonaH 63 60 After 4 Carbonizations 56 30 578 B7. 2 00 N0. 7-l0 Plant Ola after 1 Carbonization... 57 57 57! 66.0 06. 4 Fresh Clay alter l arbonization without steam... 57 50 Fresh Clay alter 4 Carbonizations without steam 56 64 576 67. 3 06. 1 Fresh Burned Clay 72 87 1040 00. 6 as. a No. 5-10 Plant Burned Clay 73 91 1042 i114 as ll Fresh Clay Burned after 15 Carhonizations. 15 81 913 81.] ill 6 Fresh Clay Burned after 2 Carbonlzatlons 75 91 i058 91.6 06. 0 Fresh Clay Burned after 10 Carbonlzationa 75 93 1063 91.4 06.0 No. 5-10 Plant Clay after 1 Carboniaatiom. 75 79 1002 88. l as 1 19B No. 10 Plant Clay after 2 Carbonitationa. 76 1064 Di. 2 96. 3 2013". Alter 4 Carbonlzatlons 76 81 M 88.2 95. 8 21C. Fresh Burned Clay 12 5 8.0 22C. Clay Burned alter 6 carbonlzatlom 12. ll 8. 0 230-,. Fresh Clay after 6 Carbonirations 1a 0 l8. 6 240 Fresh Clay after 9 Carhonizations" l2. 6 9.0

A further advantage of the present process results from the more emcient regeneration that is possible. Because of this more eflicient regeneration, smaller inventories of clay are required and consequently less capital investment. Further since the clays may be used many more times the expense for new quantities of clay is materially reduced. Moreover, the extensive classifications and bin facilities required by present day conventional methods of regeneration may be eliminated. Under the present process the clay need only be separated into two classes, that is, fresh clay and revivifled or carbonized clay.

While the invention has been described hereinbefore principally with respect to regeneration of spent clays, the invention may be made use of to increase the activity of fresh clay, Thus fresh clay may be dipped or otherwise coated with a suitable peroleum oil and then subjected to our carbonizing process, thereby giving it an activity which is greater than its original activity.

The invention has been described in detail with respect to treatment of petroleum refining clays. While clays and particularly fullers earth are by far the most commonly used solid porous adsorbcnt means for refining petroleum today, other solid adsorbent materials such as bauxite, silica gel, etc., are used to a limited extent in place of clays. It is to be understood that the present invention is also applicable to these other solid adsorbent refining materials that may be used in place of clays for refining petroleum.

This application is a continuation-impart of our co-pending application Serial No. 275,672 (abandoned) filed May 25, 1939.

We claim:

In a method of treating acid refined petroleum oils, the improvement which comprises treating said acid refined oils with a finely divided porous Certificate Patent No. 2,449,016.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 15 617,079 Catiett Jan. 3. 1899 1,314,204 Mumford Aug. 20, 1919 1,452,739 Hood Apr. 24, 1923 1,528,370 Gambel Mar. 3, 1925 1,589,532 Hoodless June 22, 1926 1,598,967 Hiller Sept. 7, 1926 1,680,903 Nashida et a]. Aug. 14, 1928 1,867,435 Adair July 12, 1932 1,943,246 Towne July 9, 1934 1,945,479 Davis Jan. 80, 1934 2 1,967,636 Towne July 24, 1934 2,127,702 Schmidt Aug. 23, 1938 2,156,591 Jacobson May 2, 1939 2,173,844 Houdry Sept. 26, 1939 2,242,639 Barton May 20, 1941 2,245,016 Simpson et a1. June 10, 1941 2,290,580 Degnen et a1. July 21, 1942 2,346,127 Simpson et al. Apr. 11, 1944 FOREIGN PATENTS Number Country Date 8,561 Great Britain May 20, 1898 195,174 Great Britain Aug. 24, 1922 287,141 Great Britain Feb. 4, 1929 492,929 Great Britain Sent. 29, 1938 of Correction September 7, 1948.

THOMAS P. SIMPSON ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 73, for the word adsorbent read adsorbed column 5, line 53,

for "at extremely read an extremely; line 70, for cays read 0 age; column 9, line 16, Table III, fourth column thereof, for 0.0 read 7.0; column 12, line 29, for and is" read and its; column 13, line 19, for peroleum read petroleum; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the casein the Patent Office.

Signed and sealed this 10th day of May, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

A further advantage of the present process results from the more emcient regeneration that is possible. Because of this more eflicient regeneration, smaller inventories of clay are required and consequently less capital investment. Further since the clays may be used many more times the expense for new quantities of clay is materially reduced. Moreover, the extensive classifications and bin facilities required by present day conventional methods of regeneration may be eliminated. Under the present process the clay need only be separated into two classes, that is, fresh clay and revivifled or carbonized clay.

While the invention has been described hereinbefore principally with respect to regeneration of spent clays, the invention may be made use of to increase the activity of fresh clay, Thus fresh clay may be dipped or otherwise coated with a suitable peroleum oil and then subjected to our carbonizing process, thereby giving it an activity which is greater than its original activity.

The invention has been described in detail with respect to treatment of petroleum refining clays. While clays and particularly fullers earth are by far the most commonly used solid porous adsorbcnt means for refining petroleum today, other solid adsorbent materials such as bauxite, silica gel, etc., are used to a limited extent in place of clays. It is to be understood that the present invention is also applicable to these other solid adsorbent refining materials that may be used in place of clays for refining petroleum.

This application is a continuation-impart of our co-pending application Serial No. 275,672 (abandoned) filed May 25, 1939.

We claim:

In a method of treating acid refined petroleum oils, the improvement which comprises treating said acid refined oils with a finely divided porous Certificate Patent No. 2,449,016.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 15 617,079 Catiett Jan. 3. 1899 1,314,204 Mumford Aug. 20, 1919 1,452,739 Hood Apr. 24, 1923 1,528,370 Gambel Mar. 3, 1925 1,589,532 Hoodless June 22, 1926 1,598,967 Hiller Sept. 7, 1926 1,680,903 Nashida et a]. Aug. 14, 1928 1,867,435 Adair July 12, 1932 1,943,246 Towne July 9, 1934 1,945,479 Davis Jan. 80, 1934 2 1,967,636 Towne July 24, 1934 2,127,702 Schmidt Aug. 23, 1938 2,156,591 Jacobson May 2, 1939 2,173,844 Houdry Sept. 26, 1939 2,242,639 Barton May 20, 1941 2,245,016 Simpson et a1. June 10, 1941 2,290,580 Degnen et a1. July 21, 1942 2,346,127 Simpson et al. Apr. 11, 1944 FOREIGN PATENTS Number Country Date 8,561 Great Britain May 20, 1898 195,174 Great Britain Aug. 24, 1922 287,141 Great Britain Feb. 4, 1929 492,929 Great Britain Sent. 29, 1938 of Correction September 7, 1948.

THOMAS P. SIMPSON ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 73, for the word adsorbent read adsorbed column 5, line 53,

for "at extremely read an extremely; line 70, for cays read 0 age; column 9, line 16, Table III, fourth column thereof, for 0.0 read 7.0; column 12, line 29, for and is" read and its; column 13, line 19, for peroleum read petroleum; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the casein the Patent Office.

Signed and sealed this 10th day of May, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

